ADVANCED CHEMISTRY 2 Philip Matthews ±m±l CAMBRIDGE UNIVERSITY PRESS
Acknowledgements How to use this book INORGANIC CHEMISTRY 88 Periodicity of physical properties 88.1 Periodicity of ionisation energies 88.2 Periodicity of atomic volume 88.3 Periodicity of atomic radius 88.4 Periodicity of melting and boiling points 88.5 Periodicity of valency 88.6 Periodicity of electronegativity 89 Periodicity of chemical properties 89.1 How this unit is arranged 89.2 How do properties change down a Group? 89.3 How do properties change across a Period? 89.4 Diagonal relationships between some elements 90 Hydrogen and hydrides 90.1 The dement 90.2 The large-scale extraction of hydrogen 90.3 The uses of hydrogen 90.4 The chemical properties of hydrogen 90.5 Hydride formation with metals 90.6 Hydride formation with non-metals 90.7 Some unusual hydrides 91 Water 91.1 What is special about water? 91.2 Some chemical reactions of water page vii viii 87 The Periodic Table 533 87.1 The origin of the Periodic Table 533 87.2 The modern Periodic Table 534 87.3 The Periodic Table and electron structures s 535 87.4 The Periodic Table, metals and non-metals 535 87.5 What are the differences between the A and B Groups? 539 543 549 552 553 554 554 555 558 558 559 91.3 91.4 91.5 91.6 91.7 92 92.1 92.2 92.3 92.4 92.5 92.6 92.7 92.8 92.9 93 93.1 93.2 93.3 93.4 93.5 93.6 94 94.1 94.2 94.3 94.4 94.5 94.6 95 95.1 95.2 95.3 95.4 95.5 96 96.1 Heavy water The water cycle Water pollution Water treatment The estimation of the amount of oxygen in water Group I Reactions with oxygen Reactions with water The hydroxides The carbonates and hydrogencarbonates The nitrates and nitrites The sulphates, hydrogensulphates and sulphites Group II and hydroxides The carbonates and hydrogencarbonates The sulphates Explaining trends in solubilities Group III The hydroxides The sulphates Carbon Why is carbon important? Where is carbon found? Carbon dioxide and carbon monoxide The importance of carbonates Carbon disulphide Group IV 560 560 561 563 566 569 569 571 572 573 573 575 575 576 577 577 578 579 582 582 584 584 585 586 586 589 589 591 591 593 594 596 596 m
96.2 96.3 96.4 96.5 96.6 96.7 96.8 97 97.1 97.2 97.3 97.4 97.5 97.6 97.7 97.8 97.9 97.10 98 98.1 98.2 98.3 98.4 98.5 98.6 98.7 98.8 99 99.1 99.2 99.3 99.4 99.5 99.6 99.7 99.8 99.9 99.10 100 100.1 100.2 100.3 100.4 100.5 100.6 100.7 100.8 100.9 101 101.1 101.2 101.3 101.4 The importance of Silicon The extraction of the elements Organic Compounds of the elements Sulphides Nitrogen The element Nitrogen, ammonia and fertilisers The place of nitrogen in Nature Ammonia and hydrazine Nitrogen oxides Nitrogen oxides and air pollution The chemistry of nitric acid Nitrates Nitrous acid and nitrites Nitrogen halides Group V The extraction of the elements and oxohalides The oxoacids The uses of phosphate salts Oxygen and oxides The element The large-scale extraction of oxygen The uses of oxygen The place of oxygen in Nature Ozone (trioxygen) Ozonolysis There are four types of oxide Typical basic oxides Typical acidic oxides Peroxides Group VI The action of heat on sulphur The extraction of sulphur Sulphuric acid and oxohalides Sulphites, sulphates and other oxoanions Group VII: the Discovery and extraction of the The laboratory preparation of the The reactivity of the 597 597 599 599 601 603 604 607 607 610 610 611 616 616 617 618 619 620 621 622 623 629 630 631 631 632 632 633 636 636 637 637 639 641 642 642 643 644 649 649 101.5 101.6 101.7 102 102.1 102.2 102.3 102.4 102.5 102.6 102.7 103 103.1 103.2 104 104.1 104.2 105 105.1 105.2 105.3 105.4 105.5 105.6 105.7 105.8 105.9 106 106.1 106.2 106.3 107 107.1 107.2 107.3 108 108.1 108.2 108.3 108.4 108.5 The are oxidising agents Reactions with water and alkali Halide ions Compounds of the The hydrogen halides Inter-halogen Compounds Metal halides Making metal halides Compounds containing oxygen and Explaining redox reactions using redox Potentials The halogen oxoacids Pseudohalides and pseudo What is a pseudohalide? Pseudo The noble gases What is special about the noble gases? Compounds of the noble gases Transition metals Transition metals and their electron structures The oxidation states of transition metals What are complex ions? The shapes of complex ions What happens to the d orbitals in a complex ion? Why are transition metal Compounds often paramagnetic? Why are transition metal Compounds often coloured? How do the transition metals act as catalysts? Transition metals and alloys More about complex ions Isomerism in complex ions Stability constants of complex ions Complexes and redox potentials Chromium, manganese and iron The chemistry of chromium The chemistry of manganese The chemistry of iron Group IIB and hydroxides The sulphates, nitrates and carbonates ORGANIC CHEMISTRY 650 651 651 654 654 657 658 659 659 661 661 667 667 668 670 670 671 673 675 677 679 681 681 683 685 685 688 689 694 697 697 698 109 Organic chemistry 705 109.1 What is organic chemistry? 705 IV
109.2 What are organic chemicals like? 109.3 The main types of organic chemical 109.4 The tetrahedral arrangement around carbon atoms 109.5 When is the arrangement of atoms around carbon not tetrahedral? 109.6 Baeyer's strain theory 109.7 Important homologous series 109.8 Naming organic Compounds 109.9 Chain isomerism 109.10 Functional group isomerism 109.11 What happens in organic reactions? 109.12 Organic analysis 110 Optical activity 110.1 What is optical activity? 110.2 Polarimeters 110.3 Why are some substances chiral? 110.4 More about tartaric acid 110.5 Properties of enantiomers and racemic mixtures 110.6 Resolution of racemic mixtures and diastereoisomers 110.7 The configurations of optical isomers 110.8 The mutarotation of glucose 111 Alkanes 111.1 The main types of hydrocarbon 111.2 The importance of alkanes 111.3 The reactions of alkanes 111.4 How to prepare alkanes 112 Alkenes and alkynes 112.1 The structure of alkenes 112.2 Ways of making alkenes 112.3 The oxidation of alkenes 112.4 The addition reactions of alkenes 112.5 Ozonolysis 112.6 Polymerisation 112.7 The oxo reaction 112.8 The structure and preparation of alkynes 112.9 The properties of alkynes 113 Aromatic hydrocarbons 113.1 What are aromatic hydrocarbons? 113.2 Ways of making arenes 113.3 The reactions of arenes 113.4 Reactions of the side chain 113.5 Addition reactions of the benzene ring 113.6 Electrophilic Substitution of benzene rings 114 More about electrophilic Substitution 114.1 How a group on a benzene ring influences electrophilic Substitution 114.2 Why do some groups activate and some deactivate the ring? 114.3 Why do some groups direct ortho/para and some meta? 705 705 707 708 710 711 713 713 721 721 722 723 725 728 733 737 737 738 739 740 744 744 746 746 747 751 751 752 754 754 755 755 762 762 763 764 114.4 115 115.1 115.2 115.3 115.4 115.5 115.6 115.7 116 116.1 116.2 116.3 116.4 116.5 116.6 116.7 117 117.1 117.2 117.3 117.4 117.5 117.6 117.7 118 118.1 Why do the behave differently to other groups? Organic halogen Compounds What are halogenoalkanes? Methods of making halogenoalkanes Halogenoalkanes are attacked by nucleophiles An elimination reaction of halogenoalkanes There are two types of aromatic halogen Compound How do we prepare halogenoarenes? What are the reactions of halogenoarenes? Alcohols The structures and uses of alcohols How we can make alcohols The oxidation reactions of alcohols Two reactions of the OH group Reactions in which the OH group is replaced by another group Dehydration reactions When alcohols react with acids, esters are made Aromatic alcohols There are two kinds of aromatic alcohol How to make phenol Why is phenol acidic? Phenol is more reactive than benzene Reactions of the OH group on phenol A test for phenol A polymerisation reaction of phenol Aldehydes and ketones Aldehydes and ketones contain a carbonyl group 118.2 The manufacture of simple aldehydes and ketones 118.3 Two methods of preparing aldehydes or ketones 118.4 Two methods of preparing aromatic aldehydes and ketones 118.5 Aldehydes and ketones undergo addition reactions 118.6 Condensation reactions 118.7 Aldehydes and ketones can be reduced 118.8 Aldehydes are good reducing agents 118.9 Ketones are hard to oxidise 118.10 Reactions with 118.11 Reaction with phosphorus pentachloride 118.12 Polymerisation reactions of aldehydes 118.13 The aldol condensation 118.14 Cannizzaro's reaction 119 Carboxylic acids 119.1 Most carboxylic acids are weak acids 119.2 Ways of making carboxylic acids 766 776 786 787 787 788 788 793 793 794 795 796 800 801 802 803 805 805 806 806 807 807 808 808 811 811 812 v
119.3 The reactions of carboxylic acids 813 119.4 The chloroethanoic acids 815 120 Carboxylic acid derivatives 818 120.1 What are the derivatives of carboxylic acids? 818 120.2 Acid Chlorides 818 120.3 Acid anhydrides 821 120.4 Amides 823 120.5 The reactions of urea, (NH 2 ) 2 CO 824 120.6 Esters 825 120.7 Nitriles 827 121 Ethers 831 121.1 What are ethers? 831 121.2 The preparation of ethers 832 121.3 The reactions of ethers 833 122 Amines 836 122.1 There are several types of amine 836 122.2 The preparation of amines 836 122.3 Amines are bases 839 122.4 Amines react with halogenoalkanes 841 122.5 The acetylation and benzoylation of amines 841 122.6 Reactions with nitrous acid at ordinary temperatures 842 122.7 Substitution reactions of diazonium ions 843 122.8 Coupling reactions of benzenediazonium ions 844 122.9 Some reactions of phenylamine and other aromatic amines 846 123 Amino acids and proteins 850 123.1 What is an amino acid? 850 123.2 Methods of making amino acids 852 123.3 Amino acids exist as dipolar ions 852 123.4 Amino acids can be both acidic and basic 852 123.5 Electrophoresis and isoelectric points 853 123.6 The geometry of amino acids 853 123.7 Amino acids use a peptide link to join together 854 123.8 Proteins 855 123.9 How to discover the structure of a protein 858 123.10 The X-ray patterns of proteins 859 123.11 How enzymes act as catalysts 860 124 Deoxyribonucleic acid (DNA) 863 124.1 The structure of DNA 863 124.2 HowDNAworks 124.3 Genetic engineering 125 Carbohydrates 125.1 What are carbohydrates? 125.2 The structures of carbohydrates 125.3 Polysaccharides 125.4 Three properties of sugars 126 Vitamins, hormones, Steroids and pharmaceuticals 126.1 Vitamins 126.2 Hormones and Steroids 126.3 Pharmaceuticals 127 127.1 127.2 127.3 128 128.1 128.2 128.3 128.4 128.5 128.6 129 129.1 129.2 129.3 130 130.1 130.2 130.3 130.4 Polymers Monomers and polymers Polymers can be made by addition reactions Condensation polymers Polymers and industry Thermoplastic and thermosetting polymers Amorphous and crystalline polymers Mechanical properties of polymers Manufacturing techniques Uses of polymers Polymers and light Fats, oils, soaps and detergents What are fats and oils? How are soaps and detergents made? How do soaps and detergents clean? Organic problems What types of problem are there? Predicting structures from percentage compositions Using Information from spectra The results of chemical reactions Appendix B Table of ionisation energies Appendix C Table of atomic masses Appendix D Values of some universal constants Appendix E Organic analysis Bibliography Examination questions Answers to examination questions Subject index Index of names 863 866 868 868 869 869 870 875 879 879 880 884 888 888 889 891 891 893 896 898 898 899 901 904 906 913 914 916 917 919 920 937 938 945 vi